Substituted ureido dioxolanes and dioxanes and their utility as herbicides

ABSTRACT

SUBSTITUTED UREIDO DIOXOLANES AND DIOXANE COMPOUNDS HAVING THE FORMULA   1-(R-N(-R&#39;&#39;)-CO-NH-),3-((-O-C(-R2)(-R3)-(CH2-C(-R6)(-R7)-   CH2)N-C(-R4)(-R5)-O-)&gt;C(-R1)-)BENZENE   IN WHICH R IS LOWER ALKYL, R &#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL AND HYDROGEN; R1, R2, R3, R4, R5 AND R7 EACH ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALKYL; R6 IS SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL, HALOALKYL, HYDROGEN, HYDROXYMETHYL, LOWER ALKOXY CARBONYLOXYMETHYL, N-LOWER ALKYL CARBANOYLOXYMETHYL AND S-LOWER ALKYLTHIOCARBONYLOXYMETHYL; AND N IS 0 OR 1. THESE COMPOUNDS ARE USEFUL AS HERBICIDES.

United States Patent Office 3,781,305 Patented Dec. 25, 1 973 3,781,305 SUBSTITUTED UREIDO DIOXOLANES AND DI- OXANES AND THEIR UTILITY AS HERBICIDES Eugene G. Teach, El Cerrito, Calif., assignor to Staufier Chemical Company, New York, N.Y. No Drawing. Filed Oct. 26, 1971, Ser. No. 192,316 Int. Cl. C07d 13/04 US. Cl. 260-3403 52 Claims ABSTRACT OF THE DISCLOSURE Substituted ureido dioxolanes and dioxane compounds having the formula in which R is lower alkyl, R is selected from the group consisting of lower alkyl and hydrogen; R R R R R and R each are independently selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl, haloalkyl, hydrogen, hydroxymethyl, lower alkoxy carbonyloxymethyl, N-lower alkyl carbamoyloxymethyl and S-lower alkylthiocar-bonyloxymethyl; and n is or 1. These compounds are useful as herbicides.

This invention relates to certain novel substituted ureido dioxolanes and dioxanes which are useful as herbicides. The compounds of the present invention are new compositions of matter and correspond to the formula Ra R:

in which R is lower alkyl, -R' is selected from the group consisting of lower alkyl and hydrogen; R R R R R and R each are independently selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower 'alkyl, haloalkyl, hydrogen, hydroxymethyl, lower alkoxy carbonyloxymethyl, N- lower alkyl carbamoyloxymethyl and lower alkylthiocarbonyloxymethyl; and n is 0 or 1.

In the above description, the following preferred embodiments are intended for the various substituents: Lower alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 6 carbon atoms, inclusive, in both straight chain and branched chain configurations, for example, methyl, ethyl, n-propyl, isopropyl,

n-butyl, isobutyl, tertiary-butyl, n-pentyl, isopentyl, neo- The compounds of this invention have been found to be active herbicides of a general type. That is, certain members of the class have been found to be herbicidally effective against a wide range of plant species. A method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area or plant locus where control is desired.

An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By a growth controlling amoun is meant an amount of compound which causes a modifying effect upon the growth of plants. Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By plants, it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions.

The compounds of the present invention are prepared by several different methods, depending upon the nature of the starting materials and products desired. Synthesis of the starting materials can be found in several references in the literature. The following method is illustrative: Meta-nitrobenzaldehyde (wherein R supra, is hydrogen), or meta-nitroacetophenone or higher phenones (wherein R supra, is lower alkyl), are reacted with a suitable.

glycol, either 1,2 or 1,3 glycol, to give the desired cyclic acetal. The corresponding cyclic acetal is reduced by conventional methods to give the corresponding metaamino compound. The meta-amino compound is reacted with an appropriate acyl halide to obtain the desired substituted anilide, dioxolane or dioxane.

Particularly more illustrative of the above generally described method will be the following specific examples. Following the examples is a table of compounds which are prepared according to the procedures described and illustrated herein.

EXAMPLE I Preparation of intermediates 2-(m-introphenyl)-5,5-dimethyl-1,3-dioxane: One hundred and six grams. (.1116 g.) of m-nitrobenzaldehyde and 71 g. of 2,2-dimethyl-l,3-propylene glycol are combined with 200 ml. of benzene and 1 g. of p-toluene sulfonic acid and refluxed under a modified Dean-Stark apparatus until no more water is collected (approximately 15 ml.). The solution is filtered and the benzene removed under reduced pressure giving 160 g. of solid, M.P. 45-47 C. This is reduced without further purification.

Z-(m-aminophenyl)-5,5-dimethyl 1,3 dioxane: Iron powder, 110 g., in a solvent consisting of 250 ml. ethyl alcohol and 200 ml. of water and 8 ml. of concentrated hydrochloric acid is heated to reflux with good mechanical stirring and 2-(m-nitrophenyl)-5,5-dirnethyl-1,3-dioxane, 166 g., is added portionwise to maintain reflux. At the conclusion of addition the temperature is allowed to fall 5-10 C. and 8 g. of 50% sodium hydroxide is added and the slurry filtered hot through a pad of diatomaceous earth. Ethyl alcohol is removed under vacuum and the product is taken up in methylene chloride solution, separated from the water, dried over magnesium sulfate and stripped to give 133 g. of product, n =l.544l.

EXAMPLE n Preparation of 2-(m-methylureidophenyl)-5,5-dimethyl- 1,4-dioxane: Fourteen and five-tenths grams (14.5 g.) of 2-(m-aminophenyl)-5,5-dimethyl-1,3-dioxane was reacted with 5 g. of methyl isocyanate in ml. of acetone. The mixture is refluxed for one hour and poured into water and the product collected by filtration. There was obtained a 3 yield of 13.2 g. of the title compound, a solid, M.P. 140- 142 C.

EXAMPLE III Preparation of 2-(m-dimethylureidophenyl) 5,5 dimethy1-1,3-dioxane: Twelve and four-tenths grams (12.4 g.) of 2- (m-amjnophenyl)-5,5-dimethyl-1,3-dioxane is dissolved in 100 m1. of acetone containing 6.5 g. of dimethyl carbamyl chloride and 9 g. of anhydrous potassium carbonate and the mixture is heated at reflux for six hours. The mixture is poured into water and the product extracted into methylene chloride solution which is washed with dilute HCl and water and dried over anhydrous magnesium sulfate. The CH CI is removed under vacuum. There was obtained 8.5 g. of the title compound, a thick liquid, n =1.5559.

EXAMPLE 1V Preparation of intermediates Z-(m-nitrophenyl)-2-methyl-1,3-dioxolane: One hundred and sixty-five grams (165 g.) of m-nitro acetophenone was combined with 62 g. of ethylene glycol in 300 ml. of benzene. One gram of ptoluene sulfonic acid was added and the mixture heated at reflux under a Dean-Stark apparatus until no more water came ofi. The product crystallized on cooling to give 204 g., M.P. 5558 C.

2-(m-aminophenyl)-2-methyl-1,3-dioxolane: Iron powder, 170 g., was slurried with 250 ml. of ethanol and 200 ml. of water and 10 ml. of concentrated hydrochloric acid was added and the mixture heated to reflux with strong stirring. The nitro compound, 2- (m-nitropheny1)-2- Compound E E P hilflmooom tdohi b1 FEE momma m b: we

gmmgmm mmommgmmommmmmommm mmmmgmmmmmmmm mmmmmmmmmmmmmmmmmmmmmmmm mmmmmmmmmmmmmmm See footnote at end of table.

methyl dioxolane was added portionwise to maintain re flux. When addition was complete, 10 g. of 50% sodium hydroxide was added and the mixture filtered to remove the iron and iron oxide. Ethanol was removed under vacu- 5 um and the product taken up in methylene chloride, separated and dried and the solvent stripped under vacuum. Yield was 145 g., M.P. 6870 C. A pure sample melted at 76-78 C.

EXAMPLE V Preparation of 2-(m-1-methy1ureido-3-phenyl)-4,4,5,5-

1-2 hours. The solvent Was stripped off under vacuum.

There was obtained 12.3 g. of the title compound, M.P. 142-144 C.

EXAMPLE VI Preparation of 2-(m-1-methyl-ureido-3 phenyl) 2- methy1-1,3-dioxolane: Fourteen and three-tenths grams (14.3 g.) of 2-(m-aminophenyl)-2-methyl-1,3-dioxolane was dissolved in 100 ml. of acetone, 5 g. of methyl is0- cyanate is added and the mixture is heated at reflux for 1 hour. The solvent is stripped ofi under vacuum. There is obtained 19.4 g. of the title compound, n =1.5522.

The following is a table of the compounds which are prepared according to the aforementioned procedures.

Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE I 00 i ll lb i EEI UIGNMMI S m i fl il i CHzO C O CzHa CHzO 0 0-15-04 CHnOCONHCHa CzH NHCOOOH: n-(hEgNHCOO CH; C520 0 O SCH; CHzOCONHCHa CHzOCONHCHs CH CH CH CH mmmmmmmmmmmuraniummmmmmgg gmmmmmmmmmmmmmm mmmmmmmmmmmmmmmmmmmmm mummmmmnumb:rdmmmmmmmmmmmmmmmmmmmmmmmmmm I- l- Hl-U-HHHH H H O Q TABLE-Continued R R R1 Ra R3 R4 Rs 11 CH H H H H H 1 H H H H H H 1 H H H H H H 1 H H H H H H 1 CH H H H H H 1 H H H H H H 1 H H H H H H 1 H H H H H H 1 CH; H H H H H 1 H H H H H H 1 H H CH CH CH3 CH CH H CH3 CH3 CH3 CH3 0 51 ll-CgHu H H CH3 CH3 CH3 CH3 0 1 Waxy solid.

'HERBICIDAL SCREENING TESTS As previously mentioned, the herein-described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling the growth of various plant species. Compounds of this invention are tested as herbicides in the following manner.

Pre-emergence herbicide test: On the day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaris sanguinalis (L.) Sc0p.), yellow foxtail (Setaria glauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L) Beauv.), California red oat (Avena sativa (L.)), redroot pigweed (Amaranthus retroflexus (L.)), Indian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.)). Ample seeds are planted to give about to 50 seedlings per row, after emergence, depending on the size of the plants. The flats are watered after planting.

The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of a solvent, such as acetone, water, alcohol or dimethylformamide, containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate). When dimethylformamide is used, only 0.5 ml. or less is used to dissolve the compound. Another solvent is used to make the volume up to 3 ml. The following day after planting, each flat is sprayed at the rate of 20 pounds of the candidate compound per 143 gallons of solution per acre. An atomizer is used to spray the solution onto the soil surface. The flats are placed in a greenhouse at 7085 F. and watered regularly by sprinkling. Two weeks after treatment, the degree of weed control is determined by comparing the amount of germination and growth of each weed in the treated flats with Weeds in several untreated control flats. The rating system is as follows:

0=no significant injury (approximately 0-10 percent control) 3 =slight injury (approximately 10-40 percent control) 6=moderate injury (approximately 40-70 percent control) 9 =severe injury or death (approximately 70-100 percent control) An activity index is used to represent the total activity on all seven weed species. The activity index is the sum of the numbers divided by 3, so that an activity index of 21 represents complete control of all seven weeds. The results of this test are reported in Table II.

Post-emergence herbicide test: Seeds of five weed species, including hairy crabgrass, watergrass, California red oats, Indian mustard, and curly dock and one crop, pinto beans (Phaseolus' vulgaris), are planted in flats as described above for pre-emergence screening. Theflats are placed in the greenhouse at 72-85 F. and watered daily with a sprinkler. After 10 to 'l4 days after planting, when the primary leaves of'the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1% Tween 20 (polyoxyethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately 20 lb./acre if all of the spray were retained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately 12.5 lb./acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per fiat by cutting oif the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not .to wet the foliage.

TABLE II.HERBICIDAL ACTIVITY SCREENING RESULTS Herbicidal activity index 1 Pre- Postemergence emergence (20 1b./a..) (12.5 lb./a.)

Compound nulmberz See footnote at end of table.

TABIJE IIContlnued Herbicidal activity index 1 l 21=70100% control of all seven plant species tested pro-emergence. 18=70-100% control of all six plant species tested post-emergence.

The compounds of the present invention are used as pro-emergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert carrier, utilizing methods wellknown to those skilled in the art, therelby making them suitable for application as dusts, sprays, or drenches and the like, in the form and manner required. The mixtures can be dispersed in Water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. An herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from 1 to approximately 50 pounds per acre.

The phytotoxic compositions of this invention employing an herbicidally effective amount of the compound described herein are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least V2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the abovedescribed compounds include, for example, 2,4-dichlorophenoxyacetic acids, 2,4,5 trichlorophenoxyacetic acid, 2 methyl 4 chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4 bis(3 methoxypropylamino) o-methyl-thio-S- triazine; 2 chloro 4 ethylamino 6 isopropylamino- S-triazine, and 2 ethylamino 4 isopropylamino-omethylmercapto-S-triazine, urea derivatives, such as 3- (3,4 dichlorophenyl) 1,1 dimethyl urea and 3-(pchlorophenyl) 1,1 dimethyl urea and acetamides such as N,N-diallyl-a-chloroacetamide, N-(a-chloroacetyDhexamethylene imine, and N,N-diethyl-a-bromoacetamide,

and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic; and thiocarbamates, such as S-propyl dipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethylcyclohexyl-ethyl-thiocarbamate, S-ethyl hexahydro 1H- azepine-l-carbothioate and the like. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow, such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed, is readily determinable by those skilled in the art.

Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended the the present invention shall only be limited by the scope of the claims.

What is claimed is:

1. A compound having the formula Ra Ra in which R is lower alkyl, R is selected from the group consisting of lower alkyl and hydrogen; R R R R R and R each are independently selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl, haloalkyl, containing fluorine or chlorine and having 1 to 4 carbon atoms, inclusive, hydrogen, hydroxymethyl, lower alkoxy carbonyloxymethyl N-lower alkyl carbamoyloxymethyl and S-lower alkylthiocarbonyloxymethyl; and n is 0 or 1.

2. A compound according to claim 1 in which R is lower alkyl; R is hydrogen; R R R R and R are each hydrogen and n is 0.

3. A compound according to claim 2 in which R is methyl.

4. A compound according to claim 2 in which R is nbutyl.

5. A compound according to claim 1 in which R is lower alkyl; R is hydrogen; R is lower alkyl; R R

R and R are each hydrogen and n is 0.

6. A compound according to claim 5 in which R is methyl and R is methyl.

7. A compound according to claim 5 in which R is n-butyl and R is methyl.

8. A compound according to claim 5 in which R is ethyl and R is methyl.

9. A compound according to claim 1 in which R is lower alkyl, R is hydrogen; R is lower alkyl; R is lower alkyl; and R R and R are each hydrogen; and n is 0.

10. A compound according to claim 9 in which R is methyl, R is methyl and R is methyl.

11. A compound according to claim 9 in which R is n-butyl, R is methyl and R is methyl.

12. A compound according to claim 1 in which R is lower alkyl, R is lower alkyl; R; is lower alkyl; R R R and R are each hydrogen; and n is 0.

13. A compound according to claim 12in which R is methyl; R is methyl and R is methyl.

14. A compound according to claim 1 in which R is lower alkyl, R is hydrogen, R is hydrogen and R R R and R are each independently lower alkyl and n is 0.

15. A compound according to claim 14 in which R is methyl, R R R and R are each independently methyl.

16. A compound according to claim 14 in which R is n-butyl R R R and R are each independently methyl.

17. A compound according to claim 1 in which R is lower alkyl; R is lower alkyl; R; is hydrogen; R R R and R are each independently lower alkyl and n is 0.

18. A compound according to claim 17 in which R is methyl; R is methyl; and R R R and R are each independently methyl.

19. A compound according to claim 1 in which R is lower alkyl; R, R R R R and R are each independently hydrogen, n is l and R is lower alkyl and R is lower alkyl.

20. A compound according to claim 19 in which R is methyl, R is methyl and (R is methyl.

21. A compound according to claim 19 in which R is n-butyl, R is methyl and R is methyl.

22. A compound according to claim 19 in which R is methyl, R is ethyl and R is ethyl.

23. A compound according to claim 19 in which R is n-butyl, R is ethyl and R is ethyl.

24. A compound according to claim 19 in which R is ethyl, R is methyl and R is methyl.

25. A compound according to claim 19 in which R is n-propyl, R is methyl and R is methyl.

26. A compound according to claim 19 in which R is methyl, R is methyl and R is ethyl.

27. A compound according to claim 19 in which R is ethyl, R is methyl and R is ethyl.

28. A compound according to claim '19 in which R is n-butyl, R is methyl and R is ethyl.

29. A compound according to claim 19 in which R is methyl, R is methyl and R is n-propyl.

30. A compound according to claim 19 in which R is ethyl, R is methyl and R is n-propyl.

31. A compound according to claim 19 in which R is n-butyl, R is methyl and R is n-propyl.

32. A compound according to claim 19 in which R is methyl, R is n-propyl and R is n-butyl.

33. A compound according to claim 19 in which R is n-butyl, R is n-propyl and R is n-butyl.

34. A compound according to claim 1 in which R is lower alkyl, R is lower alkyl, R R R R and R are each independently hydrogen, n is 1, R is lower alkyl and R is lower alkyl.

35. A compound according to claim 34 in which R is methyl, R is methyl, R is methyl and R is methyl.

36. A compound according to claim 34 in which R is methyl, R' is methyl, R is ethyl and R is ethyl.

37. A compound according to claim 34 in which R is methyl, R is methyl, R is methyl and R is ethyl.

38. A compound according to claim 34 in which R is methyl, R is methyl, R is methyl, R is n-propyl.

39. A compound according to claim 34 in which R is methyl, R is methyl, R is n-propyl and R is n-butyl.

40. A compound according to claim 1 in which R is lower alkyl, R is hydrogen, R is lower alkyl, R R R and R are each independently hydrogen, n is 1, R is lower alkyl and R is lower alkyl.

41. A compound according to claim 40 in which R is methyl, R is methyl, R is methyl and R is methyl.

42. A compound according to claim 1 in which R is lower alkyl, R is lower alkyl, R is lower alkyl, R R R and R are each independently hydrogen, n is 1, R is lower alkyl and R is lower alkyl.

43. A compound according to claim 42 in which R is methyl, R is methyl, R is methyl, R is methyl and R is methyl.

44. A compound according to claim 1 in which R is lower alkyl, R is hydrogen, R is hydrogen, R is lower alkyl, R is lower alkyl, R; is lower alkyl, R is hydrogen, n is 1, R is hydrogen and R is hydrogen.

45. A compound according to claim 44 in which R is methyl, R is methyl, R is methyl and R is methyl.

46. A compound according to claim 44 in which R is n-butyl, R is methyl, R is methyl and R is methyl.

47. A compound according to claim 1 in which R is lower alkyl, R is hydrogen, R is hydrogen, R is lower alkyl, R R and R are each independently hydrogen, n is 1, R is lower alkyl and R is lower alkyl.

48. A compound according to claim 47 in which R is methyl, R is isopropyl, R is methyl and R is methyl.

49. A compound according to claim 47 in which R is n-butyl, R is isopropyl, R is methyl and R is methyl.

50. A compound according to claim 1 in which R is methyl, R, R R R R and R are each independently hydrogen, n is 1, R is N-ethylcarbamoyloxymethyl and R is methyl.

51. A compound according to claim 1 in which R is methyl, R, R R R R and R are each independently hydrogen, n is 1, R is N-n-butylcarbamoyloxymethyl, and R is methyl.

52. A compound according to claim 1 in which R is methyl, R, R R R R and R are each independently hydrogen, R is methylthiocarbonyloxymethyl and R is methyl.

References Cited UNITED STATES PATENTS 3,641,060 2/ 1972. Nakanishi et al. 260340.7

ALEX MAZEL, Primary Examiner J. H. TURNIPSEED, Assistant Examiner US. Cl. X.R. 71-88 

